Materials, methods and techniques for generating rare earth carbonates

ABSTRACT

Mixed rare earth carbonate may be prepared by mixing a rare earth sulfate solution with a precipitating agent comprising a first sodium carbonate (Na2CO3) solution, to form a first mixture, and generating a higher sulfate rare earth carbonate wet cake from the first mixture. The higher sulfate rare earth carbonate wet cake can be mixed with a second sodium carbonate (Na2CO3) solution to form a second mixture, and a lower sulfate rare earth carbonate can be generated from the second mixture.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.63/163,566, filed Mar. 19, 2021, which is hereby incorporated in itsentirety.

TECHNICAL FIELD

The present disclosure relates to rare earth carbonates. Morespecifically, materials and methods disclosed and contemplated hereinrelate to production of rare earth carbonates with low sulfate from rareearth sulfate solutions.

INTRODUCTION

Rare earths may be obtained through the processing of mined rare earthminerals. These mined rare earth minerals are processed in a sequentialmanner until they are of a form that may be used as an input to rareearth separation processes. Monazite, a rare earth mineral, is processedby mining and acid cracking using concentrated sulfuric acid, followedby leaching in water. The output of this sequential process is a rareearth sulfate solution. Before the rare earth sulfate solution may beintroduced into a solvent extraction process to separate the rare earthelements, the rare earth sulfate solution must be converted to a rareearth chloride solution, which can be further processed to isolatevarious rare earths of interest.

Generally, three methods are currently used for producing mixed rareearth chloride solutions from mixed rare earth sulfate solutions. Afirst method involves precipitating a mixed rare earth double salt withsodium chloride (NaCl), converting the mixed rare earth double salt tomixed rare earth hydroxide with caustic soda and, downstream, dissolvingwith hydrochloric acid. A second method is to precipitate a mixed rareearth carbonate using ammonium bicarbonate and, downstream, dissolvingrare earth carbonate with hydrochloric acid (HCl). A third method is toextract the rare earths from the sulfate solution with a solventextraction process, such as using di-(2-ethylhexyl)phosphoric acid(DEPHA), and then strip the solvent using hydrochloric acid. All ofthese processes will produce a mixed rare earth chloride solution withlow sulfate content.

The instant disclosure is directed to methods of producing a mixed rareearth carbonate with low sulfate content in a continuous manner frommixed rare earth sulfate solutions using sodium carbonate. Resultingmixed rare earth carbonates can be dissolved in hydrochloric acid toproduce a mixed rare earth chloride solution, which in turn can be usedas an input to a rare earth solvent extraction process.

SUMMARY

In one aspect, a method for preparing a rare earth carbonate isdisclosed. The method may include mixing a rare earth sulfate solutionwith a precipitating agent comprising a first sodium carbonate (Na₂CO₃)solution, thereby continuously forming a first mixture; generating ahigher sulfate rare earth carbonate wet cake from the first mixture;mixing the higher sulfate rare earth carbonate wet cake with a secondsodium carbonate (Na₂CO₃) solution to form a second mixture; andgenerating a lower sulfate rare earth carbonate from the second mixture.

In another aspect, a system for generating rare earth carbonates isdisclosed. An example system may comprise a first vessel in fluidcommunication with a rare earth sulfate solution source and aprecipitating agent source, the first vessel comprising first vesselagitation apparatus; a second vessel in fluid communication with thefirst vessel, the second vessel comprising second vessel agitationapparatus; a filter unit in fluid communication with the second vessel;a third vessel in fluid communication with the filter unit and a sodiumcarbonate solution source, the third vessel comprising third vesselagitation apparatus; and a second filter unit in fluid communicationwith the third vessel.

There is no specific requirement that a material, technique or methodrelating to rare earth carbonates include all of the detailscharacterized herein to obtain some benefit according to the presentdisclosure. Thus, the specific examples characterized herein are meantto be exemplary applications of the techniques described, andalternatives are possible.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is a schematic depiction of an exemplary system forgenerating mixed rare earth carbonate.

DETAILED DESCRIPTION

Materials, methods and techniques disclosed and contemplated hereinrelate to generating mixed rare earth carbonates. Generally, exemplarymixed rare earth carbonates may be generated with precipitation andsulfate removal operations. These operations may be performed ascontinuous processes. Exemplary mixed rare earth carbonates may compriseless than about 2 wt. % sulfate.

I. Definitions

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Example methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentdisclosure. The materials, methods, and examples disclosed herein areillustrative only and not intended to be limiting.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that do not precludethe possibility of additional acts or structures. The singular forms“a,” “an” and “the” include plural references unless the context clearlydictates otherwise. The present disclosure also contemplates otherembodiments “comprising,” “consisting of” and “consisting essentiallyof,” the embodiments or elements presented herein, whether explicitlyset forth or not.

Definitions of specific functional groups and chemical terms aredescribed in more detail below. For purposes of this disclosure, thechemical elements are identified in accordance with the Periodic Tableof the Elements, CAS version, Handbook of Chemistry and Physics, 75^(th)Ed., inside cover, and specific functional groups are generally definedas described therein.

For the recitation of numeric ranges herein, each intervening numberthere between with the same degree of precision is explicitlycontemplated. For example, for the range of 6-9, the numbers 7 and 8 arecontemplated in addition to 6 and 9, and for the range 6.0-7.0, thenumber 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 areexplicitly contemplated.

The modifiers “about” or “approximately” used in connection with aquantity are inclusive of the stated value and has the meaning dictatedby the context (for example, it includes at least the degree of errorassociated with the measurement of the particular quantity). Thesemodifiers should also be considered as disclosing the range defined bythe absolute values of the two endpoints. For example, the expression“from about 2 to about 4” also discloses the range “from 2 to 4.” Theterm “about” may refer to plus or minus 10% of the indicated number. Forexample, “about 10%” may indicate a range of 9% to 11%, and “about 1”may mean from 0.9-1.1. Other meanings of “about” may be apparent fromthe context, such as rounding off, so, for example “about 1” may alsomean from 0.5 to 1.4.

II. Exemplary Materials

Exemplary methods and techniques use and generate various materials.Example materials include mixed rare earth sulfate solutions,precipitating agents comprising sodium carbonate (Na₂CO₃) solutions, andrare earth carbonates.

A. Exemplary Mixed Rare Earth Sulfate Solutions

Exemplary mixed rare earth sulfate solutions comprise one or more rareearth components dissolved in a sulfate solution. In some instances,mixed rare earth sulfate solutions are generated from Monazite cracking.Example rare earths dissolved in mixed rare earth sulfate solutions caninclude, without limitation, lanthanum, cerium, neodymium, and/orpraseodymium. In some instances, exemplary mixed rare earth sulfatesolutions comprise one or more impurities. Example impurities include,but are not limited to, silica, iron, and sodium.

In some instances, mixed rare earth sulfate solutions may have a rareearth concentration of about 5 g/L to about 45 g/L. In variousimplementations, mixed rare earth sulfate solutions may have a rareearth concentration of at least 5 g/L; at least 10 g/L; at least 15 g/L;at least 20 g/L; at least 25 g/L; at least 30 g/L; at least 35 g/L; orat least 40 g/L. In various implementations, mixed rare earth sulfatesolutions may have a rare earth concentration of no more than 45 g/L; nomore than 40 g/L; no more than 35 g/L; no more than 30 g/L; no more than25 g/L; no more than 20 g/L; no more than 15 g/L; or no more than 10g/L. In various implementations, mixed rare earth sulfate solutions mayhave a rare earth concentration of 5-45 g/L; 10-40 g/L; 15-35 g/L; or20-30 g/L.

In some instances, mixed rare earth sulfate solutions may have a pH ofabout 2.0 to about 4.5. In various implementations, mixed rare earthsulfate solutions may have a pH of at least 2.0; at least 2.5; at least3.0; at least 3.5; or at least 4.0. In various implementations, mixedrare earth sulfate solutions may have a pH of no more than 4.5; no morethan 4.0; no more than 3.5; no more than 3.0; or no more than 2.5. Invarious implementations, mixed rare earth sulfate solutions may have apH of 2.0-4.5; 2.5-4.25; 3.0-4.0; or 3.5-4.0.

B. Exemplary Sodium Carbonate Solutions

Exemplary precipitating agents typically comprise sodium carbonate(Na₂CO₃) solutions. In some instances, exemplary precipitating agentsconsist essentially of sodium carbonate (Na₂CO₃) solution. In someinstances, exemplary precipitating agents consist of sodium carbonate(Na₂CO₃) solution. Exemplary precipitating agents comprising sodiumcarbonate solution used during one or more precipitation operations aretermed “first sodium carbonate solutions” and “second sodium carbonatesolutions” for ease of discussion. The distinction between these twosolutions is described.

In some instances, a concentration of the first sodium carbonate(Na₂CO₃) solution may be about 5 wt. % to about 20 wt. %. In variousimplementations, a concentration of the first sodium carbonate (Na₂CO₃)solution may be at least 5 wt. %; at least 10 wt. %; at least 15 wt. %;or at least 18 wt. %. In various implementations, a concentration of thefirst sodium carbonate (Na₂CO₃) solution may be no more than 20 wt. %;no more than 15 wt. %; no more than 10 wt. %; or no more than 5 wt. %.In various implementations, a concentration of the first sodiumcarbonate (Na₂CO₃) solution may be 5-20 wt. %; 5-15 wt. %; or 5-10 wt.%.

In some instances, exemplary second sodium carbonate (Na₂CO₃) solutionsmay have a concentration of about 12 wt. % to about 40 wt. %. In variousimplementations, second sodium carbonate (Na₂CO₃) solutions may have aconcentration of at least 12 wt. %; at least 15 wt. %; at least 20 wt.%; at least 25 wt. %; at least 30 wt. %; or at least 35 wt. %. Invarious implementations, second sodium carbonate (Na₂CO₃) solutions mayhave a concentration of no more than 40 wt. %; no more than 35 wt. %; nomore than 30 wt. %; no more than 25 wt. %; no more than 20 wt. %; or nomore than 15 wt. %. In various implementations, second sodium carbonate(Na₂CO₃) solutions may have a concentration of 12-40 wt. %; 12-30 wt. %;or 12-20 wt. %.

C. Exemplary Rare Earth Carbonates

Exemplary systems, methods and techniques may generate higher sulfaterare earth carbonates and lower sulfate rare earth carbonates. The terms“higher” and “lower” are used solely to indicate relative sulfatecontents in different carbonates. Exemplary rare earth carbonates may begenerated as wet cakes which is defined by weight percent total rareearth oxide (TREO) concentration.

In some instances, higher sulfate rare earth carbonates may compriseabout 45 wt. % to about 72 wt. % TREO content. In variousimplementations, higher sulfate rare earth carbonates may comprise aTREO content of at least 45 wt. %; at least 50 wt. %; at least 55 wt. %;at least 60 wt. %; at least 65 wt. %; or at least 70 wt. %. In variousimplementations, higher sulfate rare earth carbonates may comprise aTREO content of no more than 72 wt. %; no more than 70 wt. %; no morethan 65 wt. %; no more than 60 wt. %; no more than 55 wt. %; or no morethan 50 wt. %. In various implementations, higher sulfate rare earthcarbonates may comprise a TREO content of 45-72 wt. %; 50-70 wt. %; or50-60 wt. %.

In some instances, higher sulfate rare earth carbonates may have a lossof ignition (LOI) of about 28% to about 55%. In various implementations,higher sulfate rare earth carbonates may have an LOI of at least 28%; atleast 30%; at least 35%; at least 40%; at least 45%; or at least 50%. Invarious implementations, higher sulfate rare earth carbonates may havean LOI of no more than 55%; no more than 50%; no more than 45%; no morethan 40%; no more than 35%; or no more than 30%. In variousimplementations, higher sulfate rare earth carbonates may have an LOI of28-55%; 30-50%; or 35-45%.

In some instances, higher sulfate rare earth carbonates may compriseabout 5 wt. % to about 25 wt. % sulfate (SO₄ ²⁻). In variousimplementations, higher sulfate rare earth carbonates may comprise atleast 5 wt. % sulfate; at least 10 wt. % sulfate; at least 15 wt. %sulfate; or at least 20 wt. % sulfate. In various implementations,higher sulfate rare earth carbonates may comprise no more than 25 wt. %sulfate; no more than 20 wt. % sulfate; no more than 15 wt. % sulfate;or no more than 10 wt. % sulfate. In various implementations, highersulfate rare earth carbonates may comprise 5-25 wt. % sulfate; 8-20 wt.% sulfate; or 10-19 wt. % sulfate.

In some instances, lower sulfate rare earth carbonate may comprisebetween 200 ppm and 2 wt. % sulfate (SO₄ ²⁻). In variousimplementations, lower sulfate rare earth carbonate may comprise atleast 200 ppm sulfate; at least 250 ppm sulfate; at least 500 ppmsulfate; at least 750 ppm sulfate; at least 1 wt. % sulfate; at least1.5 wt. % sulfate; or at least 1.75 wt. % sulfate. In variousimplementations, lower sulfate rare earth carbonate may comprise no morethan 2.0 wt. % sulfate; no more than 1.75 wt. % sulfate; no more than1.5 wt. % sulfate; no more than 1.25 wt. % sulfate; no more than 1.0 wt.% sulfate; no more than 750 ppm sulfate; no more than 500 ppm sulfate;or no more than 250 ppm sulfate. In various implementations, lowersulfate rare earth carbonate may comprise 0.02-2.0 wt. % sulfate;0.04-1.5 wt. % sulfate; 0.05-1.0 wt. % sulfate; or 0.1-1.0 wt. %sulfate.

In some instances, lower sulfate rare earth carbonate may comprisebetween 40 wt. % and 72 wt. % rare earth oxide (REO). In variousimplementations, lower sulfate rare earth carbonate may comprise atleast 40 wt. % REO; at least 50 wt. % REO; at least 55 wt. % REO; atleast 60 wt. % REO; at least 65 wt. % REO; or at least 70 wt. % REO. Invarious implementations, lower sulfate rare earth carbonate may compriseno more than 72 wt. % REO; no more than 70 wt. % REO; no more than 65wt. % REO; no more than 60 wt. % REO; no more than 55 wt. % REO; no morethan 50 wt. % REO; or no more than 45 wt. % REO. In variousimplementations, lower sulfate rare earth carbonate may comprise 40-72wt. % REO; 45-72 wt. % REO; 45-65 wt. % REO; or 50-60 wt. % REO.

III. Example Methods

Example methods for preparing rare earth carbonates disclosed andcontemplated herein can include one or more operations. Broadly,exemplary methods include one or more precipitation operations and oneor more sulfate removal operations. In various implementations, some,most, or all operations in exemplary methods may be arranged andperformed continuously (i.e., not in a batch operation).

An example method may begin by mixing a rare earth sulfate solution witha precipitating agent to form a first mixture. Exemplary precipitatingagents are described in greater detail above and comprise a first sodiumcarbonate (Na₂CO₃) solution. In some implementations, a temperature ofthe rare earth sulfate solution and/or the precipitating agent may beambient temperature.

In some instances, a temperature of the precipitating agent, prior tomixing with the rare earth sulfate solution, may be between about 25° C.and about 45° C. In various implementations, a temperature of theprecipitating agent, prior to mixing with the rare earth sulfatesolution, may be at least 25° C.; at least 30° C.; at least 35° C.; atleast 40° C.; or at least 42.5° C. In various implementations, atemperature of the precipitating agent, prior to mixing with the rareearth sulfate solution, may be no more than 45° C.; no more than 40° C.;no more than 35° C.; no more than 30° C.; or no more than 27.5° C. Invarious implementations, a temperature of the precipitating agent, priorto mixing with the rare earth sulfate solution, may be between 25° C.and 45° C.; between 25° C. and 40° C.; between 25° C. and 35° C.;between 25° C. and 30° C.; or between 27.5° C. and 32.5° C.

Flow rates of the precipitating agent and/or rare earth sulfate solutionmay be adjusted to maintain a pH of the first mixture to desired pHranges. Accordingly, exemplary methods may comprise monitoring a pH ofthe first mixture and adjusting a flow rate of the precipitating agentand/or rare earth sulfate solution to maintain a pH of the first mixtureto be within desired pH ranges. In some instances, exemplary methods maycomprise monitoring a pH of the first mixture and adjusting a flow rateof the precipitating agent while holding a flow rate of the rare earthsulfate solution constant, to maintain a pH of the first mixture to bewithin desired pH ranges.

In some implementations, a pH of the first mixture may be at least 5.0;at least 5.5; at least 6.0; at least 6.5; or at least 7.0. In someimplementations, a pH of the first mixture may be no more than 7.5; nomore than 7.0; no more than 6.5; no more than 6.0; or no more than 5.5.For instance, a pH of the first mixture may be controlled to be betweenabout 5.0 and about 7.5; between about 5.5 and about 6.5; between about5.75 and about 6.25; between about 5.9 and about 6.1; between about 5.8and about 6.0; between about 5.95 and 6.05; or between about 5.99 andabout 6.01.

In some instances, a temperature of the first mixture may be controlledto be within a desired temperature range. For example, a temperature ofthe first mixture may be controlled to be about 20° C. to about 60° C.In various implementations, a temperature of the first mixture may becontrolled to be at least about 20° C.; at least about 25° C.; at leastabout 30° C.; at least about 35° C.; at least about 40° C.; at leastabout 45° C.; at least about 50° C.; or at least about 55° C. In variousimplementations, a temperature of the first mixture may be controlled tobe no more than about 60° C.; no more than about 55° C.; no more thanabout 50° C.; no more than about 45° C.; no more than about 40° C.; nomore than about 35° C.; or no more than about 30° C. In variousimplementations, a temperature of the first mixture may be controlled tobe between 20° C. and 60° C.; between 20° C. and 45° C.; or between 20°C. and 35° C.

Exemplary rare earth sulfate solutions are mixed with precipitatingagents under agitation. Various agitation power to volume (P/V) valuesmay be used. In some implementations, an agitation speed during mixingis no less than 0.5 kw/m³; no less than 0.65 kw/m³; or no less than 0.7kw/m³. In various implementations, an agitation speed during mixing isbetween 0.5 kw/m³ and 0.7 kw/m³; between 0.5-0.65 kw/m³; between0.65-0.7 kw/m³;

Resulting mixtures comprising rare earth sulfate solution andprecipitating agent may be provided to one or more intermediate vessels,alternatively referred to as relay tanks. The one or more intermediatevessels may be agitated.

Exemplary methods may comprise monitoring and adjusting flow rates ofmixtures comprising rare earth sulfate solution and precipitating agentto maintain desired residence times. For instance, exemplary methods maycomprise providing mixtures comprising rare earth sulfate solution andprecipitating agent such that residence time in the one or moreintermediate vessels is no less than 2 hours; no less than 3 hours; noless than 4 hours; no less than 5 hours; or no less than 5.5 hours.Exemplary methods may comprise providing mixtures comprising rare earthsulfate solution and precipitating agent such that residence time in theone or more intermediate vessels is no more than 6 hours; no more than 5hours; no more than 4 hours; no more than 3.5 hours; or no more than 2.5hours. Exemplary methods may comprise providing mixtures comprising rareearth sulfate solution and precipitating agent such that residence timein the one or more intermediate vessels is between about 2 hours toabout 6 hours; about 3 hours to about 6 hours; about 3 hours to about 5hours; or about 4 hours to about 6 hours.

Resulting mixtures may be provided from the one or more intermediatevessels to one or more filtration units. In some instances, a filtrationunit may have a mesh size of about 20 μm to about 40 μm, although othersizes are contemplated.

After filtration, a higher sulfate rare earth carbonate wet cake isobtained. In some instances, the higher sulfate rare earth carbonate wetcake is washed. Water may be used for washing the higher sulfate rareearth carbonate. In various implementations, a rare earth recovery inthe higher sulfate rare earth carbonate may be at least 97%.

Next, higher sulfate rare earth carbonate wet cake is mixed with asecond sodium carbonate solution to form a second mixture. Additionaldetails about exemplary second sodium carbonate solutions are providedin greater detail above. In various instances, exemplary second sodiumcarbonate solutions have a temperature of no less than about 20° C.; noless than about 30° C.; no less than about 40° C.; no less than about50° C.; no less than about 60° C.; or no less than about 70° C. Invarious instances, exemplary second sodium carbonate solutions have atemperature of no more than about 80° C.; no more than about 70° C.; nomore than about 60° C.; no more than about 50° C.; no more than about40° C.; or no more than about 30° C. In various instances, exemplarysecond sodium carbonate solutions have a temperature between about 20°C. to about 80° C., about 25° C. to about 70° C.; about 20° C. to about50° C.; about 20° C. to about 35° C.; about 35° C. to about 65° C.; orabout 40° C. to about 60° C.

Exemplary second mixtures may be agitated for a predetermined period oftime. In various instances, exemplary second mixtures may be agitatedfor at least 1 hour; at least 2 hours; at least 3 hours; at least 4hours; at least 5 hours; at least 6 hours; at least 7 hours; at least 8hours; or at least 9 hours. In various instances, exemplary secondmixtures may be agitated for no more than 10 hours; no more than 9hours; no more than 8 hours; no more than 7 hours; no more than 6 hours;no more than 5 hours; no more than 4 hours; no more than 3 hours; or nomore than 2 hours. In various instances, exemplary second mixtures maybe agitated for about 1 hour to about 10 hours; about 2 hours to about 8hours; or about 2 hours to about 6 hours.

Exemplary second mixtures may be agitated at various agitation powers.For instance, exemplary second mixtures may be agitated at a power tovolume (P/V) ratio of at least 0.7 kw/m³. In some instances, exemplarysecond mixtures may be agitated with an agitation speed of at least 200rpm; at least 275 rpm; at least 300 rpm; at least 350 rpm; at least 400rpm; or at least 425 rpm. In some instances, exemplary second mixturesmay be agitated with an agitation speed of no more than 440 rpm; no morethan 400 rpm; no more than 375 rpm; no more than 325 rpm; no more than300 rpm; or no more than 250 rpm. In some instances, exemplary secondmixtures may be agitated with an agitation speed of 200 rpm to 440 rpm;250 rpm to 350 rpm; 275 rpm to 325 rpm; 200 rpm to 250 rpm; or 400 rpmto 440 rpm.

A solids content of exemplary second mixtures may be controlled to bewithin particular ranges. In various instances, exemplary secondmixtures may be controlled to have a solids content of no less than 10%;no less than 20%; no less than 30%; no less than 40%; no less than 50%;or no less than 60%. In various instances, exemplary second mixtures maybe controlled to have a solids content of about 10% to about 70%.

After mixing the second mixture for a predetermined period of time, anaqueous fluid may be added to the second mixture. In some instances, theaqueous fluid is water. Then the second mixture is provided to anotherfiltration unit to generate a lower sulfate rare earth carbonate. Insome instances, the lower sulfate rare earth carbonate may be washed. Insome instances, filtering the second mixture may also include recoveringsodium carbonate.

IV. Example Systems

FIG. 1 shows an exemplary system 100 for preparing rare earthcarbonates. Exemplary system 100 includes vessel 106, vessel 110, filterunit 114, vessel 120, and filter unit 126. System 100 is configured suchthat one or more operations are performed continuously. Various processcomponents, such as pumps, motors, valves, etc., are not shown forsimplicity. Other embodiments may include more or fewer components.

Vessel 106 is in fluid communication with rare earth sulfate solutionsource 102 and precipitating agent source 104. Rare earth sulfatesolution source 102 provides rare earth sulfate solution, described ingreater detail above, to vessel 106 and may include one or more flowregulation units. Precipitating agent source 104 provides precipitatingagent, described in greater detail above, to vessel 106 and may includeone or more flow regulation units.

In some instances, vessel 106 includes pH monitoring equipment that maybe in communication with flow regulation units that can adjust a flowrate from rare earth sulfate solution source 102 and/or precipitatingagent source 104. As discussed in greater detail above, a pH of thefirst mixture in vessel 106 may be controlled to be between about 5.5 toabout 6.5.

Vessel 106 includes agitation components arranged to mix rare earthsulfate solutions and precipitating agents. As discussed in greaterdetail above, an agitation power to volume (P/V) ratio in vessel 106 maybe at least 0.5 kw/m³; at least 0.65 kw/m³; or at least 0.7 kw/m³.

Vessel 106 may include temperature regulation components, such asheating or cooling jackets, to maintain a fluid temperature within adesired range. Exemplary fluid temperatures for mixtures in vessel 106are described in greater detail above. A mixture 108 comprising rareearth sulfate solution and precipitating agent is provided to vessel110.

Vessel 110 serves as a relay tank between vessel 106, where mixingoccurs, and filter unit 114. That is, mixture 112 is provided fromvessel 110 to filter unit 114. Vessel 110 may include temperatureregulation components, such as heating or cooling jackets, to maintain afluid temperature within a desired range. Exemplary fluid temperaturesfor mixtures in vessel 110 are described in greater detail above.

Filter unit 114 generates a solids portion, higher sulfate rare earthcarbonate 118, and a liquid portion, filtrate 116, from mixture 112.Liquid filtrate 116 may be discarded or processed and portions reusedfor precipitating agent source 104.

Vessel 120 is in fluid communication with second sodium carbonatesolution source 122 and solids output 118 from filter unit 114. Vessel120 may include temperature regulation components, such as heating orcooling jackets, to maintain a fluid temperature within a desired range.

Vessel 120 includes agitation components arranged to mix the highersulfate rare earth carbonate and the second sodium carbonate solution.As discussed in greater detail above, an agitation power to volume ratioin vessel 1206 may be at least 0.7 kw/m³.

After a predetermined residence time, mixture 124 is provided to filterunit 126. In some instances, mixture 124 is washed (not shown in theFIGURE) before being provided to filter unit 126. Washing of mixture 124may be conducted in an intermediate unit positioned downstream of vessel120 and filter unit 126.

Filter unit 126 generates a lower sulfate rare earth carbonate 128 and aliquid filtrate 130 from mixture 124. In some instances, the liquidfiltrate 130 may be further processed in a sodium carbonate recoveryunit (not shown in the FIGURE). Recovered sodium carbonate may be reusedfor precipitating agent source 104.

V. Experimental Examples

Experimental examples of precipitation and sulfate removal operationswere conducted, and the results are discussed below.

A. Precipitation Operations

Five experimental examples were conducted for precipitation operations.

1. Raw Materials and Chemicals

Details about the rare earth sulfate solutions and the sodium carbonatesolutions (precipitating agent) are provided in Table 1 below.

TABLE 1 Raw materials and chemical concentrations for precipitationoperation experimental examples. Example 1 Example 2 Example 3 Example 4Example 5 Rare earth sulfate Concentration 22.0 22.0 22.0 20.3 20.3solutions (g/l) pH 3.7 3.7 3.7 3.6 3.6 Na₂CO₃ solutions Concentration50.0 50.0 50.0 50.0 50.0 (g/l)

2. Process Conditions

The rare earth sulfate solutions and sodium carbonate solutions werecombined in a first vessel and agitated. The first vessel contents weremaintained to have a temperature of 30° C.+/−2° C. An overhead agitatorwas used for mixing. Then the mixture was provided to a relay tank,filtered, and washed. Table 2 below provides details for the fiveexperimental examples.

TABLE 2 Process parameters for experimental precipitation operations.Example 1 Example 2 Example 3 Example 4 Example 5 Temperature (° C.)28-32 28-32 28-32 28-32 28-32 pH 6 6 6 6 6 Agitation Speed 700 700 700700 700 (rpm) Process Flow rate Rare earth 330 330 330 330 330 sulphate(ml/hr) Na₂CO₃ 66 66 66 66 66 (ml/hr) Duration Hours (hr) 5.8 5.8 3.55.6 5.6 Filtration Pressure 4.5 4.5 4.5 4.5 4.5 (kPa)

3. Precipitation Operations Results

Each example's generated high sulfate rare earth carbonate was analyzedby Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES)and Loss on Ignition (LOI).

TABLE 3 Results from experimental precipitation operations. ExampleExample Example Example Example Analytical Results 1 2 3 4 5 Mix rareearth carbonate (g) 73.18 77.91 47.92 71.22 76.03 Rare earth oxide (REO)content (wt. %) 57.5% 54.0% 53.0% 52.6% 49.3% Sulfate (SO₄ ²⁻) content(wt. %) 11.95% 15.10% 18.38% 9.75% 9.11%

B. Sulfate Removal Operations

Five experimental examples were conducted for sulfate removaloperations.

1. Raw Materials and Chemicals

Details about the sodium carbonate solutions and higher sulfate mixedrare earth carbonates are provided in Table 3 below.

TABLE 4 Raw materials and chemical concentrations for sulfate removaloperation experimental examples. Raw materials & Chemical Example 6Example 7 Example 8 Example 9 Example 10 Na₂CO₃ Solution Concentration200 200 200 200 200 (g/l) Mix RE carbonate REO (%) 54.0% 53.0% 53.0%63.7% 55.4% SO₄ ²⁻ (%) 15.1% 18.4% 18.4% 12.0% 8.3%

2. Process Conditions

The higher sulfate rare earth carbonates and sodium carbonate solutionswere combined in a third vessel and agitated. A magnetic stirrer wasused for mixing. Then the mixture was filtered and washed. Table 5 belowprovides details for the five experimental examples.

TABLE 5 Process parameters for experimental sulfur removal operations.Example 6 Example 7 Example 8 Example 9 Example 10 Mass of Mix RE g 5050 50 50 50 Carbonate Volume ml 70 70 70 70 70 Agitation rpm 210 210 210400 430 Temperature ° C. 35 +/− 1 45 +/− 1 35 +/− 1 45 +/− 1 25 +/− 1Duration hours (hr) 4.0 2.0 4.0 4.0 2.0 Filtration Pressure 4.5 4.5 4.54.5 4.5 (kPa) Washing Water (l) 0.5 0.5 0.5 0.5 0.5

3. Sulfur Removal Operations Results

Each example's generated lower sulfate rare earth carbonate was analyzedby Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES)and Loss on Ignition (LOI). The results are shown below in Table 6.

TABLE 6 Results from experimental sulfur removal operations. AnalyticalResults Example 6 Example 7 Example 8 Example 9 Example 10 REO % 53.4%47.4% 52.5% 41.1% 40.9% SO₄ ²⁻ % 0.21% 0.09% 0.04% 0.07% 1.13%

VI. Pilot-Scale Examples

Pilot-scale examples of rare earth carbonate precipitation and sulfateremoval operations were conducted, and the results are discussed below.

1. Generation of Mixed Rare Earth Carbonate from Mixed Rare EarthSulfate and Sodium Carbonate with Both Typical Impurity Levels.

A. Raw Materials and Chemicals

The mixed rare earth sulfate solution was taken directly from rare earthsolvent extraction plant into the intermediate bulk container (IBC) inthe pilot unit. The mixed rare earth sulfate solution had REOconcentrations between 10-40 g/L and pH between 2.0 to 4.5. Levels ofimpurities were roughly 500 ppm Al and 25 ppm Fe.

The sodium carbonate solution of 5 wt. % to 10 wt. % was preparedseparately and then pumped into the designated IBC in the pilot unit.The sodium carbonate solution had sulfate impurities of 17 ppm.

B. Continuous Precipitation of Mixed Rare Earth Carbonate

Co-addition precipitation occurred on a bulk scale in the IBCprecipitation reactor with agitation by mixing rare earth sulfate withthe sodium carbonate solution. The temperature was uncontrolled andranged between 20° C. and 35° C. The slurry pH was maintained during theprecipitation process in the range from 5.8 to 6.0. Rare earth sulfateflow rates were maintained at a ratio of 5:1 for rare earth sulfate tosodium carbonate solution, 208 L/hr and sodium carbonate flow rates, 42L/hr, respectively. The flow rate of sodium carbonate was adjusted fromthis ratio only to maintain the slurry pH within 5.8 to 6.0 range.

As the solid slurry was generated, it was allowed to continuouslyoverflow from the precipitation reactor IBC into a slurry overflow IBC.A portion of the supernatant (approx. 25-75%) was removedsemi-continuously by siphoning off the supernatant, which increased thesolids content from approximately 5% to 10% wt./wt. solids. Theconcentrated slurry was filtered in a batch mode using a stand-alonecylindrical filter press (Essa® type). To quantify the filterability ofthe slurry, the filtration time and pressure were fixed at 2 hours and 5bar respectively, with a filter cake generation rate of 2500 gallons perday (gpd). After filtration, the mixed rare earth carbonate solids had arare earth oxide (REO) content of 50 wt. % to 58 wt. % and sulfateconcentration of 7 wt. % to 13 wt. %. The filter cake results from thepilot test are shown below in Table 7.

TABLE 7 Results for the continuous precipitation of mixed rare earthcarbonate from the co-addition of mixed rare earth sulfate and sodiumcarbonate with normal impurity levels. Each analytical result representsthe analysis of filter cakes generated from a single day pilot run.Analytical Results Example 11a Example 11b Example 11c Example 11dExample 11e REO wt. % 57.96 50.49 55.03 50.95 54.52 SO₄ ²⁻ wt. % 13.002611.6590 7.7218 11.5494 11.3445

C. Sulphate Removal from Mixed Rare Earth Carbonate Solids with SodiumCarbonate

The mixed rare earth carbonate solids from the process above in Step Bwas then contacted a second sodium carbonate solution with concentrationof 20 wt. % to make a slurry mixture of 700 g per liter. Mixing of theslurry was performed for 4 hours at an ambient temperature of 20 to 35°C. This slurry was then filtered using a filter press to isolate the wetsolids. The wet solids were then re-pulped in a third sodium carbonatesolution of 5 wt % to make a slurry mixture of approximately 500 g perliter. Mixing of this slurry was performed for 1 hour at a targettemperature of 40° C. or 60° C. with agitation speed of 300 rpm. Thefinal slurry was then filtered using a filter press to isolate the wetsolids, and then washed one time with deionized water (approximately 1:2ratio of solids:liquid), and then filtered until semi-moist. Theresulting solids were then analyzed for sulfate impurities by ICP-OES.

TABLE 7 Results for the laboratory scale work up of mixed rare earthcarbonate with normal impurity levels. Each analytical result representsthe analysis of same filter cake sample generated from a single daypilot run in Step B. Example 12 Example 13 Treatment Temperature ° C. 4060 REO % 50.27 35.31 La₂O₃/REO % 22.75 22.21 CeO₂/REO % 50.25 51.05Pr₆O₁₁/REO % 5.18 5.05 Nd₂O₃/REO % 17.29 17.02 Sm₂O₃/REO % 2.43 2.43 Al% 0.86 0.46 Fe % 0.23 0.07 Na % 5.7 5.8 SO₄ ²⁻ % 0.43 0.18

More than 97% of the rare earth oxide content was recovered from theoverall process in these examples.

Exemplary Embodiments

For reasons of completeness, various aspects of the technology are setout in the following numbered embodiments:

Embodiment 1: A method for preparing a rare earth carbonate, the methodcomprising:

mixing a rare earth sulfate solution with a precipitating agentcomprising a first sodium carbonate (Na₂CO₃) solution, therebycontinuously forming a first mixture;

generating a higher sulfate rare earth carbonate wet cake from the firstmixture;

mixing the higher sulfate rare earth carbonate wet cake with a secondsodium carbonate (Na₂CO₃) solution to form a second mixture; and

generating a lower sulfate rare earth carbonate from the second mixture.

Embodiment 2. The method according to embodiment 1, wherein generatingthe higher sulfate rare earth carbonate wet cake from the first mixturecomprises:

-   -   agitating the first mixture;    -   controlling a pH of the first mixture to be about 5.5 to about        6.5; and    -   filtering the first mixture.        Embodiment 3. The method according to embodiment 1 or 2, wherein        a solids content of the second mixture is 10% to about 70%; and        wherein generating the lower sulfate rare earth carbonate from        the second mixture comprises:    -   agitating the second mixture for a predetermined period of time;    -   adding an aqueous fluid to the second mixture; and    -   filtering the second mixture aqueous fluid combination.        Embodiment 4. The method according to any one of embodiments        1-3, wherein each operation is performed continuously.        Embodiment 5. The method according to any one of embodiments        1-4, wherein the rare earth sulfate solution has a rare earth        concentration of about 5 g/L to about 45 g/L;

wherein a concentration of the first sodium carbonate (Na₂CO₃) solutionis about 5 wt. % to about 20 wt. %;

wherein a total rare earth oxide (TREO) content of the higher sulfaterare earth carbonate wet cake is about 45% to about 72%;

wherein a Loss of Ignition (LOI) of the higher sulfate rare earthcarbonate wet cake is about 28% to about 55%; and

wherein a sulfate content of the higher sulfate rare earth carbonate wetcake is about 5% to about 25%.

Embodiment 6. The method according to any one of embodiments 1-5,wherein an agitation power to volume (P/V) for agitating the firstmixture is no less than 0.5 kw/m³;

wherein a temperature of the first mixture during agitating is about 20°C. to about 60° C.; and

wherein an agitation speed for agitating the second mixture is between200 rpm and 440 rpm.

Embodiment 7. The method according to embodiment 6, wherein thepredetermined period of time is 1 hour to 10 hours.Embodiment 8. The method according to any one of embodiments 1-7,wherein a concentration of the second sodium carbonate (Na₂CO₃) solutionis about 12 wt. % to about 40 wt. %; and

wherein a temperature of the second sodium carbonate (Na₂CO₃) solutionis about 20° C. to about 80° C.

Embodiment 9. The method according to any one of embodiments 1-8,further comprising recovering sodium carbonate (Na₂CO₃) during filteringthe second mixture aqueous fluid combination; and

wherein the precipitating agent consists essentially of sodiumcarbonate.

Embodiment 10. The method according to any one of embodiments 1-9,wherein the pH of the first mixture is controlled to be more than 9.0;

wherein the temperature of the second sodium carbonate solution is 25°C. to 70° C.

wherein a concentration of the second sodium carbonate (Na₂CO₃) solutionis 12 wt. % to 20 wt. %;

wherein the predetermined period of time is about 2 hours to about 6hours; and

wherein a solids content of the second mixture is about 10% to about70%.

Embodiment 11. The method according to any one of embodiments 1-10,wherein a recovery of the rare earth carbonate solids is greater than97%;

wherein the lower sulfate rare earth carbonate comprises between 200 ppmand 2 wt. % sulfate (SO₄ ²⁻); and

wherein the lower sulfate rare earth carbonate comprises between 45 wt.% and 72 wt. % rare earth oxide.

Embodiment 12. The method according to any one of embodiments 1-11,further comprising:

before generating the higher sulfate rare earth carbonate wet cake,providing the first mixture to one or more intermediate vessels,

wherein a residence time in the one or more intermediate vessels is fromabout 3 hours to about 6 hours.

Embodiment 13. A rare earth carbonate material generated using themethod according to any one of embodiments 1-12.Embodiment 14. A system for preparing rare earth carbonates, the systemcomprising:

a first vessel in fluid communication with a rare earth sulfate solutionsource and a precipitating agent source, the first vessel comprisingfirst vessel agitation apparatus;

a second vessel in fluid communication with the first vessel, the secondvessel comprising second vessel agitation apparatus;

a filter unit in fluid communication with the second vessel;

a third vessel in fluid communication with the filter unit and a sodiumcarbonate solution source, the third vessel comprising third vesselagitation apparatus; and

a second filter unit in fluid communication with the third vessel.

Embodiment 15. The system according to embodiments 14, the first vesselfurther comprising pH monitoring equipment configured to monitor a pH ofa first mixture in the first vessel, the pH monitoring equipment incommunication with one or more flow regulation units configured toadjust a flow rate of the rare earth sulfate solution source and theprecipitating agent source.Embodiment 16. The system according to embodiments 14 or 15, the filterunit generating a solids portion comprising higher sulfate rare earthcarbonate and a liquid portion comprising filtrate, the filter unitbeing configured to provide the solids portion to the third vessel.Embodiment 17. The system according to any one of embodiments 14-16,further comprising a sodium carbonate recovery unit,

the second filter unit generating a lower sulfate rare earth carbonateand a liquid filtrate; the second filter unit providing the liquidfiltrate to a sodium carbonate recovery unit.

Embodiment 18. The system according to any one of embodiments 14-17, thefirst vessel comprising temperature regulation components configured tomaintain a first vessel fluid temperature between about 20° C. to about60° C.Embodiment 19. The system according to any one of embodiments 14-18, thesecond vessel comprising temperature regulation components configured tomaintain a second vessel fluid temperature between about 20° C. to about80° C.Embodiment 20. The system according to any one of embodiments 14-19, thefirst vessel agitation apparatus configured to agitate the first vesselcontents at a power to volume ratio of 0.5 kw/m³ to 0.7 kw/m³; and

the third vessel agitation apparatus configured to agitate the thirdvessel contents at a power to volume ratio of 0.5 kw/m³ to 0.7 kw/m³.

It is understood that the foregoing detailed description andaccompanying examples are merely illustrative and are not to be taken aslimitations upon the scope of the disclosure. Various changes andmodifications to the disclosed embodiments will be apparent to thoseskilled in the art. Such changes and modifications, including withoutlimitation those relating to the chemical structures, substituents,derivatives, intermediates, syntheses, compositions, formulations, ormethods of use, may be made without departing from the spirit and scopeof the disclosure.

1-12. (canceled)
 13. A rare earth carbonate material generated using amethod comprising: mixing a rare earth sulfate solution with aprecipitating agent comprising a first sodium carbonate (Na₂CO₃)solution, thereby continuously forming a first mixture; generating ahigher sulfate rare earth carbonate wet cake from the first mixture;mixing the higher sulfate rare earth carbonate wet cake with a secondsodium carbonate (Na₂CO₃) solution to form a second mixture; andgenerating a lower sulfate rare earth carbonate from the second mixture.14. A system for generating rare earth carbonates, the systemcomprising: a first vessel in fluid communication with a rare earthsulfate solution source and a precipitating agent source, the firstvessel comprising first vessel agitation apparatus; a second vessel influid communication with the first vessel, the second vessel comprisingsecond vessel agitation apparatus; a filter unit in fluid communicationwith the second vessel; a third vessel in fluid communication with thefilter unit and a sodium carbonate solution source, the third vesselcomprising third vessel agitation apparatus; and a second filter unit influid communication with the third vessel.
 15. The system according toclaim 14, the first vessel further comprising pH monitoring equipmentconfigured to monitor a pH of a first mixture in the first vessel, thepH monitoring equipment in communication with one or more flowregulation units configured to adjust a flow rate of the rare earthsulfate solution source and the precipitating agent source.
 16. Thesystem according to claim 14, the filter unit generating a solidsportion comprising higher sulfate rare earth carbonate and a liquidportion comprising filtrate, the filter unit being configured to providethe solids portion to the third vessel.
 17. The system according toclaim 16, further comprising a sodium carbonate recovery unit, thesecond filter unit generating a lower sulfate rare earth carbonate and aliquid filtrate; and the second filter unit providing the liquidfiltrate to a sodium carbonate recovery unit.
 18. The system accordingto claim 14, the first vessel comprising temperature regulationcomponents configured to maintain a first vessel fluid temperaturebetween about 20° C. to about 60° C.
 19. The system according to claim18, the second vessel comprising temperature regulation componentsconfigured to maintain a second vessel fluid temperature between about20° C. to about 80° C.
 20. The system according to claim 14, the firstvessel agitation apparatus configured to agitate the first vesselcontents at a power to volume ratio of 0.5 kw/m³ to 0.7 kw/m³; and thethird vessel agitation apparatus configured to agitate the third vesselcontents at a power to volume ratio of 0.5 kw/m³ to 0.7 kw/m³.